Norbornane skeleton structure-containing organosilicon compound and method of producing same

ABSTRACT

Disclosed are a radiation-polymerizable functional group-containing organosilicon compound, including (A) a norbornane skeleton structure, (B) a hydrolyzable silyl group bonded directly to the norbornane skeleton structure, and (C) a radiation-polymerizable functional group bonded to the norbornane skeleton structure, either directly or via a carbon atom, a hetero atom, or a combination thereof, and a method of producing the radiation-polymerizable functional group-containing organosilicon compound. Also disclosed are a haloalkyl group-containing organosilicon compound, including (D) a norbornane skeleton structure, (E) a hydrolyzable silyl group bonded directly to the norbornane skeleton structure, and (F) a haloalkyl group, which is bonded directly to the norbornane skeleton structure and either contains or does not contain a hetero atom, and a method of producing the haloalkyl group-containing organosilicon compound. These organosilicon compounds are useful as silane coupling agents having superior heat resistance stability.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a novel organosilicon compoundcomprising a radiation-polymerizable functional group or a haloalkylgroup, a norbornane skeleton structure, and a hydrolyzable silyl group,as well as a method of producing such an organosilicon compound.

2. Description of the Prior Art

Organosilicon compounds having a hydrolyzable silyl group generallygenerate a silanol group in the presence of water, and this silanolgroup is able to react with a hydroxyl group on the surface of aninorganic material, meaning the organosilicon compound can be used forsurface treatment of the inorganic material. Furthermore, organosiliconcompounds of this type that also comprise an organic functional groupthat reacts with organic resins are widely used as silane couplingagents, organic and inorganic resin modifiers, adhesion assistants andadditives, and the use and application of such compounds is well known,with numerous patent applications having been filed.

In a typical silane coupling agent, the hydrolyzable silyl group sitethat reacts with inorganic materials and the organic functional groupsite that reacts with organic resins are almost always linked via alinear hydrocarbon chain. However, the treated item obtained byconducting treatment with the silane coupling agent is frequently usedunder high-temperature conditions, and the low heat resistance of thelinear hydrocarbon chain under such conditions often creates problems.

Against this background, a norbornane skeleton structure, which is apolycyclic hydrocarbon skeleton structure, is a three dimensionallyrigid structure, and it is known that incorporating this skeletonstructure into the structure of an organic polymer increases the heatresistance of the polymer.

In conventional silane coupling agents, the incorporation of afunctional group such as an acryloyl group, methacryloyl group, epoxygroup, amino group or mercapto group as an organic group that reactswith organic resins is well known, and such silane coupling agents areused in all manner of applications.

SUMMARY OF THE INVENTION

The present invention has been developed in light of the abovecircumstances, and has an object of providing a novel organosiliconcompound in which a norbornane skeleton structure that contributes toheat resistance stability is incorporated into the linking regionbetween a hydrolyzable silyl group and a radiation-polymerizablefunctional group or haloalkyl group that functions as an organicfunctional group, as well as providing a method of producing theorganosilicon compound.

As a result of intensive investigation aimed at achieving the aboveobject, the inventors of the present invention developed anorganosilicon compound in which a hydrolyzable silyl group and either aradiation-polymerizable functional group or a haloalkyl group are linkedvia a norbornane skeleton structure. The inventors also developed amethod of producing such a compound, and they were thus able to completethe present invention.

In other words, a first aspect of the present invention provides aradiation-polymerizable functional group-containing organosiliconcompound, comprising:

(A) a norbornane skeleton structure,

(B) a hydrolyzable silyl group bonded directly to the norbornaneskeleton structure, and

(C) a radiation-polymerizable functional group bonded to the norbornaneskeleton structure, either directly or via a carbon atom, a hetero atom,or a combination thereof.

A second aspect of the present invention provides a method of producinga radiation-polymerizable functional group-containing organosiliconcompound comprising

(A) a norbornane skeleton structure,

(B) a hydrolyzable silyl group bonded directly to the norbornaneskeleton structure, and

(C) a radiation-polymerizable functional group bonded to the norbornaneskeleton structure, either directly or via a carbon atom, a hetero atom,or a combination thereof,

the method comprising:

reacting a haloalkyl group-containing organosilicon compound, comprising

(D) a norbornane skeleton structure,

(E) a hydrolyzable silyl group bonded directly to the norbornaneskeleton structure, and

(F) a haloalkyl group, which is bonded directly to the norbornaneskeleton structure, and either contains or does not contain a heteroatom, with

at least one salt having a radiation-polymerizable functional group,selected from the group consisting of alkali metal salts of organicacids having a radiation-polymerizable functional group and alkalineearth metal salts of organic acids having a radiation-polymerizablefunctional group,

at a temperature within a range from 50 to 150° C.

A third aspect of the present invention provides a haloalkylgroup-containing organosilicon compound, comprising:

(D) a norbornane skeleton structure,

(E) a hydrolyzable silyl group bonded directly to the norbornaneskeleton structure, and

(F) a haloalkyl group, which is bonded directly to the norbornaneskeleton structure, and either contains or does not contain a heteroatom.

A fourth aspect of the present invention provides a method of producinga haloalkyl group-containing organosilicon compound comprising

(D) a norbornane skeleton structure,

(E) a hydrolyzable silyl group bonded directly to the norbornaneskeleton structure, and

(F) a haloalkyl group, which is bonded directly to the norbornaneskeleton structure, and either contains or does not contain a heteroatom, the method comprising:

subjecting a hydrolyzable silane having a hydrogen atom bonded directlyto a silicon atom, and a norbornene derivative having a norborneneskeleton structure and a haloalkyl group that is bonded directly to thenorbornene skeleton structure and either contains or does not contain ahetero atom, to a hydrosilylation reaction in the presence of acatalyst.

Because the radiation-polymerizable functional group-containingorganosilicon compound of the present invention includes a rigidpolycyclic hydrocarbon skeleton structure, namely a norbornane skeletonstructure, as the unit that links the hydrolyzable silyl group and theradiation-polymerizable functional group, the organosilicon compoundexhibits superior heat resistance stability to conventional compoundscontaining a linear hydrocarbon chain as this linking unit. Furthermore,the radiation-polymerizable functional group-containing organosiliconcompound of the present invention contains a radiation-polymerizablefunctional group that functions as an organic functional group havingsuperior reactivity with organic resins. Accordingly, theradiation-polymerizable functional group-containing organosiliconcompound of the present invention is useful as a silane coupling agenthaving improved heat resistance stability.

Similarly, because the haloalkyl group-containing organosilicon compoundof the present invention also includes a rigid polycyclic hydrocarbonskeleton structure, namely a norbornane skeleton structure, as the unitthat links the hydrolyzable silyl group and the haloalkyl group, thisorganosilicon compound also exhibits superior heat resistance stabilityto conventional compounds containing a linear hydrocarbon chain as thislinking unit. Accordingly, the haloalkyl group-containing organosiliconcompound of the present invention is itself useful as a silane couplingagent having improved heat resistance stability. Moreover, because allmanner of organic functional groups can be introduced at the haloalkylgroup of the haloalkyl group-containing organosilicon compound of thepresent invention, this organosilicon compound is also useful as aprecursor to a multitude of silane coupling agents having excellent heatresistance stability.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagram showing the ¹H NMR spectrum of the reaction productof an example 1.

FIG. 2 is a diagram showing the ¹³C NMR spectrum of the reaction productof the example 1.

FIG. 3 is a diagram showing the ²⁹Si NMR spectrum of the reactionproduct of the example 1.

FIG. 4 is a diagram showing the ¹H NMR spectrum of the reaction productof an example 3.

FIG. 5 is a diagram showing the ¹³C NMR spectrum of the reaction productof the example 3.

FIG. 6 is a diagram showing the ²⁹Si NMR spectrum of the reactionproduct of the example 3.

FIG. 7 is a diagram showing the ¹H NMR spectrum of the reaction productof an example 5.

FIG. 8 is a diagram showing the ¹³C NMR spectrum of the reaction productof the example 5.

FIG. 9 is a diagram showing the ²⁹Si NMR spectrum of the reactionproduct of the example 5.

FIG. 10 is a diagram showing the IR spectrum of the reaction product ofthe example 5.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

A more detailed description of the present invention is provided below.

[Radiation-Polymerizable Functional Group-Containing OrganosiliconCompound]

A radiation-polymerizable functional group-containing organosiliconcompound of the present invention comprises:

(A) a norbornane skeleton structure,

(B) a hydrolyzable silyl group bonded directly to the norbornaneskeleton structure, and

(C) a radiation-polymerizable functional group bonded to the norbornaneskeleton structure, either directly or via a carbon atom, a hetero atom,or a combination thereof.

<(A) Norbornane Skeleton Structure>

The structure (A) is a norbornane skeleton structure. In thisdescription, a “norbornane skeleton structure” refers to an atomgrouping that remains when 2 to 12 hydrogen atoms are removed fromnorbornane, and provided this definition is satisfied, there are nolimitations on the number of hydrogen atoms removed or the positions ofthose hydrogen atoms.

Examples of this norbornane skeleton structure of the structure (A)include norbornylene groups represented by a structural formula shownbelow:

namely, divalent hydrocarbon groups generated by removing the hydrogenatoms from position 2 or 3, and position 5 or 6 of norbornane.

<(B) Hydrolyzable Silyl Group>

The structure (B) is a hydrolyzable silyl group that is bonded directlyto the norbornane skeleton structure of the structure (A). In thisdescription, there are no particular limitations on the hydrolyzablesilyl group, provided it is a silyl group that contains at least one ofa monovalent hydrolyzable atom bonded directly to the silicon atom (anatom that generates a silanol group upon reaction with water) and amonovalent hydrolyzable group bonded directly to the silicon atom (agroup that generates a silanol group upon reaction with water). Thistype of hydrolyzable silyl group generates a silanol group uponhydrolysis, and this silanol group undergoes a dehydration-condensationwith an inorganic material, forming a chemical bond represented by aformula: Si—O-M (wherein, M represents the inorganic material). Theradiation-polymerizable functional group-containing organosiliconcompound of the present invention may include either a singlehydrolyzable silyl group of the structure (B), or two or more suchhydrolyzable silyl groups, and if two or more hydrolyzable silyl groupsexist, these groups may be either the same or different.

Examples of the hydrolyzable silyl group of the structure (B) includesilyl groups represented by a general formula (1′) shown below, as wellas a chlorosilyl group, bromosilyl group, methoxysilyl group,ethoxysilyl group, propoxysilyl group, butoxysilyl group or phenoxysilylgroup.

<(C) Radiation-Polymerizable Functional Group>

The structure (C) is a radiation-polymerizable functional group bondedto the norbornane skeleton structure of the structure (A), eitherdirectly or via a carbon atom, a hetero atom, or a combination thereof.Upon irradiation, the radiation-polymerizable functional group of thestructure (C) reacts or copolymerizes with an organic resin to form abond. The radiation-polymerizable functional group-containingorganosilicon compound of the present invention may include either asingle radiation-polymerizable functional group of the structure (C), ortwo or more such radiation-polymerizable functional groups, and if twoor more radiation-polymerizable functional groups exist, the groups maybe either the same or different. In this description, in those caseswhere the radiation-polymerizable functional group of the structure (C)is bonded to the norbornane skeleton structure of the structure (A) viaa carbon atom, a hetero atom or a combination thereof, the term “linkinggroup” is used to describe the structure that links the structures (A)and (C).

In this description, “radiation” includes electromagnetic radiation suchas microwaves, infrared radiation, ultraviolet (UV) radiation, X-raysand γ-rays, as well as particle beams such as α-beams, proton beams,electron beams and neutron beams.

Examples of the radiation-polymerizable functional group include anacryloyl group, methacryloyl group, styryl group or vinyl group, and ofthese, an acryloyl group or methacryloyl group or the like is preferred.

Examples of the hetero atom include an oxygen atom, sulfur atom ornitrogen atom. In those cases where the linking group includes a heteroatom, the linking group may include either a single hetero atom or twoor more hetero atoms, and in the case of two or more hetero atoms, theseatoms may be either the same or different. The hetero atom exists withina structure such as a carbonyl group (—C(═O)—), oxy group (—O—), thiogroup (—S—), imino group (—NH—) or nitro group (—N<).

Specific examples of the linking group include divalent groups such asalkylene groups that either contain or do not contain a hetero atom, acarbonyl group, an oxy group, a thio group, an imino group, orcombinations thereof.

Examples of the combination of the radiation-polymerizable functionalgroup of the structure (C) and the linking group include monovalentgroups represented by a general formula (1″) shown below.

<Other Structures>

The radiation-polymerizable functional group-containing organosiliconcompound of the present invention may also include other structuresbesides the structures (A) to (C), provided the inclusion of these otherstructures does not impair the object of the present invention. If suchother structures are included, then the radiation-polymerizablefunctional group-containing organosilicon compound of the presentinvention may include either a single such structure, or two or moresuch structures, and if two or more such other structures exist, thesestructures may be either the same or different. Specific examples ofthese other structures include alkyl groups of 1 to 10 carbon atoms suchas a methyl group, ethyl group, propyl group, isopropyl group, butylgroup, isobutyl group, tert-butyl group, pentyl group, hexyl group,heptyl group, octyl group, nonyl group or decyl group.

<Examples of the Radiation-Polymerizable Functional Group-ContainingOrganosilicon Compound>

There are no particular restrictions on the radiation-polymerizablefunctional group-containing organosilicon compound of the presentinvention, provided it includes all of the structures (A) to (C).However, in terms of enhancing the heat resistance stability of theorganosilicon compound of the present invention, the carbon atom withinthe structure (A) to which the structure (B) is directly bonded ispreferably different from the carbon atom within the structure (A) towhich the structure (C) is bonded, either directly or via the linkinggroup. Particularly preferred compounds include those in which thestructure (B) is bonded to either the carbon atom at position 2 orposition 3, or the carbon atom at position 5 or position 6 of thestructure (A), and the structure (C) is bonded, either directly or viathe linking group, to the other position to which the structure (B) isnot bonded.

Examples of preferred forms of the radiation-polymerizable functionalgroup-containing organosilicon compound of the present invention includeorganosilicon compounds represented by a general formula (1) shownbelow:

(wherein, each X represents, independently, a halogen atom, an alkoxygroup of 1 to 10 carbon atoms, a phenyloxy group, or an acetoxy group,

Y represents an acryloyloxy group or a methacryloyloxy group,

R¹ represents an alkyl group of 1 to 10 carbon atoms,

R² represents an alkylene group of 1 to 10 carbon atoms that eithercontains, or does not contain, an oxygen atom, a sulfur atom, a nitrogenatom, or a combination thereof, and

m represents an integer from 0 to 2).

Of the compounds represented by the general formula (1), the silyl groupportion represented by the general formula (1′) shown below correspondswith the hydrolyzable silyl group of the structure (B):

(wherein, X, R¹ and m are as defined above),whereas the portion represented by the general formula (1″) shown belowcorresponds with the combination of the radiation-polymerizablefunctional group of the structure (C) and the linking group:—R²—Y  (1″)(wherein, Y and R² are as defined above).

In those cases where X is a halogen atom, examples include a fluorineatom, chlorine atom, bromine atom or iodine atom.

In those cases where X is an alkoxy group, the group contains from 1 to10 carbon atoms, typically from 1 to 8 carbon atoms, preferably from 1to 6 carbon atoms, and more preferably from 1 to 4 carbon atoms.Specific examples of the alkoxy group include a methoxy group, ethoxygroup, propoxy group, isopropoxy group, butoxy group, isobutoxy group,tert-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group,octyloxy group, nonyloxy group or decyloxy group.

The group X is preferably a methoxy group or ethoxy group.

The group R¹ contains from 1 to 10 carbon atoms, typically from 1 to 8carbon atoms, preferably from 1 to 6 carbon atoms, and more preferablyfrom 1 to 4 carbon atoms. Examples of R¹ include a methyl group, ethylgroup, propyl group, isopropyl group, butyl group, isobutyl group,tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group,nonyl group or decyl group. Of these, a methyl group or ethyl group ispreferred.

The group R² contains from 1 to 10 carbon atoms, typically from 1 to 8carbon atoms, preferably from 1 to 6 carbon atoms, and more preferablyfrom 1 to 3 carbon atoms.

In those cases where R² does not include an oxygen atom, sulfur atom,nitrogen atom or a combination thereof, specific examples of R² includealkylene groups such as a methylene group, ethylene group,methylmethylene group, propylene group (trimethylene group ormethylethylene group), butylene group (such as a tetramethylene group,1,2-butylene group, 1,3-butylene group or 2,3-butylene group), pentenegroup (such as a pentamethylene group), hexene group (such as ahexamethylene group), heptene group (such as a heptamethylene group),octene group (such as an octamethylene group), nonene group (such as anonamethylene group) or decene group (such as a decamethylene group). Ofthese, linear alkylene groups such as methylene group, ethylene group,trimethylene group, tetramethylene group, pentamethylene group,hexamethylene group, heptamethylene group, octamethylene group,nonamethylene group or decamethylene group are preferred, and amethylene group is particularly desirable.

In those cases where R² contains an oxygen atom, sulfur atom, nitrogenatom or a combination thereof, specific examples of R² include divalentgroups represented by the formulas shown below.—(CH₂)_(a)—C(═O)—(CH₂)_(b)——(CH₂)_(c)—O—(CH₂)_(d)——(CH₂)_(c)—S—(CH₂)_(d)——(CH₂)_(e)—N((CH₂)_(f)H)—(CH₂)_(g)—(wherein, a and b each represents an integer from 1 to 8, provided thata+b is an integer from 2 to 9, c and d each represents an integer from 1to 9, provided that c+d is an integer from 2 to 10, e and g eachrepresents an integer from 1 to 9, and f represents an integer from 0 to8, provided that e+f+g is an integer from 2 to 10.)

m is an integer from 0 to 2, and is typically 0.

More preferred examples of the radiation-polymerizable functionalgroup-containing organosilicon compound of the present invention includeorganosilicon compounds represented by a general formula (2) shownbelow:

(wherein, X, Y, R¹ and m are as defined above, and n represents aninteger from 1 to 10).

n represents an integer from 1 to 10, preferably an integer from 1 to 8,more preferably an integer from 1 to 6, and even more preferably aninteger from 1 to 3.

Particularly preferred examples of the radiation-polymerizablefunctional group-containing organosilicon compound of the presentinvention include organosilicon compounds represented by a generalformula (3) shown below:

(wherein, X, Y, R¹ and m are as defined above).

Specific examples of the radiation-polymerizable functionalgroup-containing organosilicon compound of the present invention includethe compounds shown below.

(wherein, R represents a hydrogen atom or a methyl group.)

The radiation-polymerizable functional group-containing organosiliconcompound of the present invention may be either a pure compound or amixture of isomers. Examples of possible isomeric mixtures includemixtures containing an endo isomer and an exo isomer, and mixtures ofregioisomers. Examples of regioisomeric mixtures include a mixture ofisomers in which, in the general formula (1), the position on thenorbornane skeleton structure to which the hydrolyzable silyl group ofthe structure (B) is directly bonded is a mixture of position 2 andposition 3, and a mixture of isomers in which, in the general formula(1), the position on the norbornane skeleton structure to which theradiation-polymerizable functional group of the structure (C) isdirectly or indirectly bonded is a mixture of position 5 and position 6.

[Haloalkyl Group-Containing Organosilicon Compound]

A haloalkyl group-containing organosilicon compound of the presentinvention comprises:

(D) a norbornane skeleton structure,

(E) a hydrolyzable silyl group bonded directly to the norbornaneskeleton structure, and

(F) a haloalkyl group, which is bonded directly to the norbornaneskeleton structure, and either contains or does not contain a heteroatom.

<(D) Norbornane Skeleton Structure>

The definition, configuration, and specific examples of the norbornaneskeleton structure of the structure (D) are as described above in thesection entitled “<(A) Norbornane Skeleton Structure>”.

<(E) Hydrolyzable Silyl Group>

The structure (E) is a hydrolyzable silyl group that is bonded directlyto the norbornane skeleton structure of the structure (D). The haloalkylgroup-containing organosilicon compound of the present invention mayinclude either a single hydrolyzable silyl group of the structure (E),or two or more such hydrolyzable silyl groups, and if two or morehydrolyzable silyl groups exist, these groups may be either the same ordifferent. Specific examples of the hydrolyzable silyl group of thestructure (E) are as described above in the section entitled “<(B)Hydrolyzable Silyl Group>”.

<(F) Haloalkyl Group>

The structure (F) is a haloalkyl group that is bonded directly to thenorbornane skeleton structure of the structure (D), and either containsor does not contain a hetero atom. The haloalkyl group of the structure(F) reacts or copolymerizes with an organic resin to form a bond. Thehaloalkyl group-containing organosilicon compound of the presentinvention may include either a single haloalkyl group of the structure(F), or two or more such haloalkyl groups, and if two or more haloalkylgroups exist, the groups may be either the same or different.

Examples of the hetero atom include an oxygen atom, sulfur atom ornitrogen atom. The haloalkyl group of the structure (F) may includeeither a single hetero atom or two or more hetero atoms, and in the caseof two or more hetero atoms, these atoms may be either the same ordifferent. The hetero atom exists between two of the carbon atoms thatconstitute the haloalkyl group of the structure (F), for example, in theform of a carbonyl group (—C(═O)—), oxy group (—O—), thio group (—S—) orimino group (—NH—). Alternatively, the hetero atom may exist betweenthree carbon atoms in the form of a nitro group (—N<) or the like.

Examples of the haloalkyl group of the structure (F) include haloalkylgroups represented by a general formula (4″) shown below.

<Other Structures>

The haloalkyl group-containing organosilicon compound of the presentinvention may also include other structures besides the structures (D)to (F), provided the inclusion of these other structures does not impairthe object of the present invention. If such other structures areincluded, then the haloalkyl group-containing organosilicon compound ofthe present invention may include either a single such structure, or twoor more such structures, and if two or more such other structures exist,these structures may be either the same or different. Specific examplesof these other structures are as described above in the section entitled“<Other Structures>” within the description of the“[Radiation-polymerizable Functional Group-containing OrganosiliconCompound]”.

<Examples of the Haloalkyl Group-Containing Organosilicon Compound>

There are no particular restrictions on the haloalkyl group-containingorganosilicon compound of the present invention, provided it includesall of the structures (D) to (F). However, in terms of enhancing theheat resistance stability of the organosilicon compound of the presentinvention, the hydrolyzable silyl group of the structure (E) and thehaloalkyl group of the structure (F) are preferably bonded directly tomutually different carbon atoms on the norbornane skeleton structure ofthe structure (D). Compounds in which one of the structures (E) and (F)is bonded directly to the carbon atom at position 2 or position 3, andthe other structure is bonded directly to the carbon atom at position 5or position 6 are particularly desirable.

Examples of preferred forms of the haloalkyl group-containingorganosilicon compound of the present invention include organosiliconcompounds represented by a general formula (4) shown below:

(wherein, X, R¹, R² and m are as defined above, and Z represents ahalogen atom).

Of the compounds represented by the general formula (4), the silyl groupportion represented by the general formula (4′) shown below correspondswith the hydrolyzable silyl group of the structure (E):

(wherein, X, R¹ and m are as defined above),whereas the portion represented by the general formula (4″) shown belowcorresponds with the haloalkyl group of the structure (F):—R²—Z  (4″)(wherein, Z and R² are as defined above).

The group X is preferably a chlorine atom, a methoxy group or an ethoxygroup.

Examples of the group Z include a fluorine atom, chlorine atom, bromineatom or iodine atom, and of these, a chlorine atom or bromine atom ispreferred.

More preferred examples of the haloalkyl group-containing organosiliconcompound of the present invention include organosilicon compoundsrepresented by a general formula (5) shown below:

(wherein, X, Z, R¹, m and n are as defined above).

Particularly preferred examples of the haloalkyl group-containingorganosilicon compound of the present invention include organosiliconcompounds represented by a general formula (6) shown below:

(wherein, X, R¹ and m are as defined above, and Z′ represents a bromineatom or a chlorine atom).

Specific examples of the haloalkyl group-containing organosiliconcompound of the present invention include the compounds shown below.

The haloalkyl group-containing organosilicon compound of the presentinvention may be either a pure compound or a mixture of isomers.Examples of possible isomeric mixtures include mixtures containing anendo isomer and an exo isomer, and mixtures of regioisomers. Examples ofregioisomeric mixtures include a mixture of isomers in which, in thegeneral formula (4), the position on the norbornane skeleton structureto which the hydrolyzable silyl group of the structure (E) is directlybonded is a mixture of position 2 and position 3, and a mixture ofisomers in which, in the general formula (4), the position on thenorbornane skeleton structure to which the haloalkyl group of thestructure (F) is directly bonded is a mixture of position 5 and position6.

[Method of Producing Radiation-Polymerizable Functional Group-ContainingOrganosilicon Compound]

The radiation-polymerizable functional group-containing organosiliconcompound of the present invention comprising the structures (A) to (C)can be produced, for example, by conducting a desalting reaction betweena haloalkyl group-containing organosilicon compound, comprising

(D) a norbornane skeleton structure,

(E) a hydrolyzable silyl group bonded directly to the norbornaneskeleton structure, and

(F) a haloalkyl group, which is bonded directly to the norbornaneskeleton structure, and either contains or does not contain a heteroatom, and

at least one salt having a radiation-polymerizable functional group,selected from the group consisting of alkali metal salts of organicacids having a radiation-polymerizable functional group and alkalineearth metal salts of organic acids having a radiation-polymerizablefunctional group,

at a temperature within a range from 50 to 150° C.

<Haloalkyl Group-Containing Organosilicon Compound>

The haloalkyl group-containing organosilicon compound is as describedabove. There are no particular restrictions on the haloalkyl group ofthe structure (F), provided it is capable of producing aradiation-polymerizable functional group of the structure (C) via thedesalting reaction with the salt having a radiation-polymerizablefunctional group. In those cases where the targeted organosiliconcompound is an organosilicon compound represented by the above generalformula (1), a compound represented by the above general formula (4) canbe used as the haloalkyl group-containing organosilicon compound. Inthose cases where the targeted organosilicon compound is anorganosilicon compound represented by the above general formula (2), acompound represented by the above general formula (5) can be used as thehaloalkyl group-containing organosilicon compound. In those cases wherethe targeted organosilicon compound is an organosilicon compoundrepresented by the above general formula (3), a compound represented bythe above general formula (6) can be used as the haloalkylgroup-containing organosilicon compound.

<Salt Having a Radiation-Polymerizable Functional Group>

The salt having a radiation-polymerizable functional group is at leastone salt selected from the group consisting of alkali metal salts oforganic acids having a radiation-polymerizable functional group andalkaline earth metal salts of organic acids having aradiation-polymerizable functional group. Examples of the organic acidshaving a radiation-polymerizable functional group include acrylic acidand methacrylic acid. Examples of the alkali metals include lithium,sodium and potassium, and sodium and potassium are preferred. Examplesof the alkaline earth metals include calcium, strontium and barium, andcalcium is preferred.

Examples of the salt having a radiation-polymerizable functional groupinclude acrylic acid salts and methacrylic acid salts represented by ageneral formula (10) shown below:Y-M  (10)(wherein, Y is as defined above, and M represents an alkali metal atomor an alkaline earth metal atom), namely, alkali metal salts andalkaline earth metal salts of acrylic acid and methacrylic acid.Specific examples of the acrylic acid salts and methacrylic acid saltsrepresented by the general formula (10) include potassium acrylate,potassium methacrylate, sodium acrylate, sodium methacrylate, lithiumacrylate and lithium methacrylate. Of these, from the viewpoint ofreactivity, potassium acrylate, potassium methacrylate, sodium acrylateand sodium methacrylate are preferred, and potassium acrylate andpotassium methacrylate are particularly desirable.

<Conditions for Desalting Reaction>

There are no particular restrictions on the blend ratio between thehaloalkyl group-containing organosilicon compound and the salt having aradiation-polymerizable functional group, although in terms ofreactivity and productivity, the reaction is preferably conducted usinga quantity of the salt having a radiation-polymerizable functional groupthat is within a range from 0.8 to 2 mols, and preferably from 0.8 to1.2 mols, per 1 mol of the haloalkyl group-containing organosiliconcompound.

In the synthesis of the radiation-polymerizable functionalgroup-containing organosilicon compound of the present invention, thedesalting reaction is preferably conducted under heating and within anorganic solvent in order to accelerate the reaction rate.

The organic solvent is preferably an organic solvent that contains noactive hydrogen, and of such solvents, polar organic solvents areparticularly desirable. Specific examples of the organic solvent includesaturated hydrocarbon-based solvents such as pentane, hexane,cyclohexane, heptane and decane; ether-based solvents such as diethylether, tetrahydrofuran and dioxane; ester-based solvents such as ethylacetate and butyl acetate; polyether-based solvents such as triethyleneglycol dimethyl ether; aromatic solvents such as benzene, toluene andxylene; ketone-based solvents such as acetone, methyl ethyl ketone, andmethyl isobutyl ketone; and amide-based solvents such as formamide anddimethylformamide. Of these organic solvents, dimethylformamide andtoluene are particularly preferred in terms of the degree of polarityand the boiling point. A single organic solvent may be used alone, or acombination of two or more different solvents may be used.

The reaction temperature must be set within the range from 50 to 150°C., and is preferably from 80 to 130° C. If the temperature is lowerthan 50° C., then the desalting reaction tends to proceed poorly,whereas if the temperature exceeds 150° C., there is a possibility thatthe produced radiation-polymerizable functional group-containingorganosilicon compound may polymerize.

When conducting the reaction, a polymerization inhibitor is preferablyused to stabilize the produced radiation-polymerizable functionalgroup-containing organosilicon compound. Typical commercially availableproducts may be used as this polymerization inhibitor, and hinderedphenol-based compounds are particularly desirable. The quantity added ofthe polymerization inhibitor need only be a typical quantity for apolymerization inhibitor. For example, a quantity of 0.001 to 1.0% bymass relative to the radiation-polymerizable functional group-containingorganosilicon compound is preferred.

<Purification Method>

The alkali metal halide or alkaline earth metal halide generated as aresult of the desalting reaction can be separated from the targetradiation-polymerizable functional group-containing organosiliconcompound using techniques such as filtration that are well known tothose skilled in the art. The radiation-polymerizable functionalgroup-containing organosilicon compound can be further purified usingmethods such as distillation under reduced pressure or liquid columnchromatography that are also well known to those skilled in the art.

[Method of Producing Haloalkyl Group-Containing Organosilicon Compound]

<Production Method 1>

The haloalkyl group-containing organosilicon compound comprising thestructures (D) to (F) can be produced, for example, by subjecting ahydrolyzable silane having a hydrogen atom bonded directly to thesilicon atom (hereafter also referred to as a “SiH group”), and anorbornene derivative having a norbornene skeleton structure and ahaloalkyl group that is bonded directly to the norbornene skeletonstructure and either contains or does not contain a hetero atom, to ahydrosilylation reaction in the presence of a catalyst.

Hydrolyzable Silane Having a SiH Group

There are no particular restrictions on the hydrolyzable silane having aSiH group, provided it is capable of generating a hydrolyzable silylgroup of the structure (E) via a hydrosilylation reaction with the abovenorbornene derivative.

In those cases where the haloalkyl group-containing organosiliconcompound is an organosilicon compound represented by one of the generalformulas (4) to (6) shown above, examples of the hydrolyzable silanehaving a SiH group include compounds represented by a general formulashown below:

(wherein, X, R¹ and m are as defined above).

Norbornene Derivative

The norbornene derivative has a norbornene skeleton structure and ahaloalkyl group that is bonded directly to the norbornene skeletonstructure and either contains or does not contain a hetero atom. In thisdescription, a “norbornene skeleton structure” refers to an atomgrouping that remains when at least one hydrogen atom are removed from astructure in which a carbon-carbon double bond is formed between atleast one pair of adjacent carbon atoms within norbornane. Provided thevalency of the norbornene skeleton structure is monovalent or higher,there are no particular restrictions on the number of carbon-carbondouble bonds or on the position of each double bond.

The norbornene derivative may include either a single haloalkyl group ortwo or more haloalkyl groups within the norbornene skeleton structure,and if two or more haloalkyl groups exist, these groups may be eitherthe same or different.

Examples of the hetero atom and its configuration within the haloalkylgroup are as described above in the section entitled “<(F) HaloalkylGroup>”.

In those cases where the haloalkyl group-containing organosiliconcompound is an organosilicon compound represented by the above generalformula (4), examples of the norbornene derivative include compoundsrepresented by a general formula (7) shown below:

(wherein, R² and Z are as defined above).

In those cases where the haloalkyl group-containing organosiliconcompound is an organosilicon compound represented by the above generalformula (5), compounds represented by the general formula (7) in whichR² is a —(CH₂)_(n)— group can be used as the norbornene derivative.Furthermore, in those cases where the haloalkyl group-containingorganosilicon compound is an organosilicon compound represented by theabove general formula (6), compounds represented by the general formula(7) in which R is a —CH₂— group and Z is Z′ can be used as thenorbornene derivative.

The norbornene derivative may use a compound commercially available fromany of the various chemical manufacturers, or may use a reaction productobtained using a conventional method in which an olefin compound capableof generating the haloalkyl group and cyclopentadiene are subjected to aDiels Alder reaction. For example, a norbornene derivative representedby the above general formula (7) can be prepared in accordance with thisconventional method by subjecting an olefin compound represented by ageneral formula shown below:CH₂═CH—R²—Zand cyclopentadiene to a Diels Alder reaction.

<Production Method 2>

Among the haloalkyl group-containing organosilicon compound comprisingthe structures (D) to (F), an organosilicon compound comprising:

(D) a norbornane skeleton structure,

(E′) an organooxysilyl group bonded directly to the norbornane skeletonstructure, and

(F) a haloalkyl group, which is bonded directly to the norbornaneskeleton structure, and either contains or does not contain a heteroatom can be produced by:

using a halosilane having a SiH group as the hydrolyzable silane havinga SiH group from the production method 1, conducting the hydrosilylationreaction of the production method 1 to obtain an organosilicon compoundcomprising:

(D) a norbornane skeleton structure,

(E″) a halosilyl group bonded directly to the norbornane skeletonstructure, and

(F) a haloalkyl group, which is bonded directly to the norbornaneskeleton structure, and either contains or does not contain a heteroatom,

and then following the hydrosilylation reaction, reacting theorganosilicon compound comprising (D), (E″) and (F) with a hydroxylgroup-containing organic compound.

Organosilicon Compound Comprising Structures (D), (E′) and (F)

With the exception of restricting the structure (E) to the structure(E′), the organosilicon compound comprising the structures (D), (E′) and(F) is the same as the organosilicon compound comprising the structures(D) to (F).

The structure (E′) is an organooxysilyl group that is bonded directly tothe norbornane skeleton structure of the structure (D). Theorganosilicon compound comprising the structures (D), (E′) and (F) mayinclude either a single organooxysilyl group of the structure (E′), ortwo or more such organooxysilyl groups, and if two or moreorganooxysilyl groups exist, the groups may be either the same ordifferent.

Examples of the organosilicon compound comprising the structures (D),(E′) and (F) include compounds represented by a general formula (8)shown below:

(wherein, each X′ represents, independently, an alkoxy group of 1 to 10carbon atoms, a phenyloxy group or an acetoxy group, and Z, R¹, R² and mare as defined above).

In those cases where X′ represents an alkoxy group, the typical andpreferred ranges for the number of carbon atoms within the group, andspecific examples of the alkoxy group are as described above for thegroup X.

Halosilane Having a SiH Group

There are no particular restrictions on the halosilane having a SiHgroup, provided it is capable of generating a halosilyl group of thestructure (E″) via a hydrosilylation reaction with the above norbornenederivative.

In those cases where the haloalkyl group-containing organosiliconcompound is an organosilicon compound represented by the above generalformula (8), compounds represented by a general formula shown below canbe used as the halosilane.

(wherein, X″ represents a halogen atom, and R¹ and m are as definedabove.)

Organosilicon Compound Comprising Structures (D), (E″) and (F)

With the exception of restricting the structure (E) to the structure(E″), the organosilicon compound comprising the structures (D), (E″) and(F) is the same as the organosilicon compound comprising the structures(D) to (F).

The structure (E″) is an halosilyl group that is bonded directly to thenorbornane skeleton structure of the structure (D). The organosiliconcompound comprising the structures (D), (E″) and (F) may include eithera single halosilyl group of the structure (E″), or two or more suchhalosilyl groups, and if two or more halosilyl groups exist, the groupsmay be either the same or different.

In those cases where the haloalkyl group-containing organosiliconcompound is an organosilicon compound represented by the above generalformula (8), examples of the organosilicon compound comprising thestructures (D), (E″) and (F) include compounds represented by a generalformula (9) shown below:

(wherein, X″, Z, R¹, R² and m are as defined above).

Hydroxyl Group-Containing Organic Compound

There are no particular restrictions on the hydroxyl group-containingorganic compound, provided it reacts with the halosilyl group of thestructure (E″) to generate the organooxysilyl group of the structure(E′). Examples of the hydroxyl group-containing compound includealcohols, phenols and carboxylic acids.

In those cases where the haloalkyl group-containing organosiliconcompound is an organosilicon compound represented by the above generalformula (8), examples of the hydroxyl group-containing organic compoundinclude compounds represented by a general formula shown below:X′—H(wherein, X′ is as defined above).Of these compounds, methanol and ethanol are preferred.

<Reaction Conditions>

Hydrosilylation Reaction

In a hydrosilylation reaction, the use of a catalyst composed of a heavymetal complex or the like is conventional, and in the hydrosilylationreaction within the production method of the present invention, a heavymetal complex such as a palladium complex, platinum complex or rhodiumcomplex is typically used as a catalyst. Of these complexes, in terms ofthe reactivity and the quantity of catalyst used, a palladium complex ora platinum complex is preferred, and from the viewpoint of reactivity, apalladium complex is particularly desirable.

Although there are no particular restrictions on the quantity ofcatalyst used, from the viewpoints of reactivity and productivity, thequantity is typically within a range from 0.000001 to 0.01 mols, andpreferably from 0.00001 to 0.001 mols, per 1 mol of the norbornenederivative. Provided the quantity of the catalyst is within this range,a satisfactory reaction acceleration effect that corresponds with thequantity of the catalyst is readily obtained.

There are no particular restrictions on the blend ratio between thehydrolyzable silane having a SiH group and the norbornene derivative,but from the viewpoints of reactivity and productivity, a quantity ofthe hydrolyzable silane having a SiH group within a range from 0.5 to 2mols, and particularly from 0.8 to 1.2 mols, is preferably reacted witheach 1 mol of the norbornene derivative.

During the hydrosilylation reaction, in addition to the catalystdescribed above, an auxiliary agent that controls the catalyzed reactionmay also be added. Conventional materials may be used as this auxiliaryagent, and specific examples include organophosphorus compounds,phosphite ester compounds, and organonitrogen compounds.

The hydrosilylation reaction is usually conducted as a solventlessreaction, although solvent dilution may be used to facilitate reactioncontrol. In such cases, there are no particular restrictions on thesolvent, provided it exhibits no reactivity with the raw materials usedand has no other adverse effects such as catalyst poisoning. Specificexamples of the solvent include hydrocarbon-based solvents such aspentane, hexane, cyclohexane, benzene, toluene and xylene; ether-basedsolvents such as diethyl ether, tetrahydrofuran and dioxane; ester-basedsolvents such as ethyl acetate and butyl acetate; aprotic polar solventssuch as acetonitrile and dimethylformamide; and chlorinated hydrocarbonsolvents such as dichloromethane and chloroform. A single solvent may beused alone, or a combination of a plurality of different solvents may beused.

Although there are no particular restrictions on the reactiontemperature, provided it is a temperature at which the hydrosilylationproceeds, the temperature is typically within a range from 0 to 200° C.,and preferably from 10 to 150° C.

Organooxylation Reaction

In this description, the term “organooxylation reaction” describes thereaction following the hydrosilylation reaction of the above productionmethod 2, wherein the organosilicon compound comprising the structures(D), (E″) and (F) is reacted with the hydroxyl group-containing organiccompound, thereby converting the halosilyl group of the structure (E″)to the organooxysilyl group of the structure (E′). Specifically, inthose cases where the hydroxyl group-containing organic compound is analcohol, the organooxylation reaction refers to an alkoxylationreaction. More specifically, if the hydroxyl group-containing organiccompound is methanol, then the organooxylation reaction refers to amethoxylation reaction.

The organooxylation reaction proceeds spontaneously even without acatalyst, although from the viewpoints of reactivity and productivity,the reaction is preferably conducted in the presence of urea, a tertiaryamine or a metal alkoxide or the like, which acts as a scavenger for thegenerated hydrogen halide.

Although there are no particular restrictions on the quantity of thisscavenger, from the viewpoints of reactivity and productivity, thequantity is typically within a range from 0.5 to 1.5 mols, andpreferably from 0.8 to 1.2 mols, per 1 mol of halogen atoms within thestructure (E″) of the organosilicon compound comprising the structures(D), (E″) and (F). Provided the quantity of the scavenger is within thisrange, a satisfactory reaction acceleration effect that corresponds withthe quantity of the scavenger is readily obtained.

There are no particular restrictions on the blend ratio between theorganosilicon compound comprising the structures (D), (E″) and (F) andthe hydroxyl group-containing organic compound, but from the viewpointsof reactivity and productivity, the blend quantity is preferablyadjusted so that the quantity of hydroxyl groups within the hydroxylgroup-containing organic compound is within a range from 1 to 3 mols,and particularly from 1 to 2 mols, per 1 mol of halogen atoms within thestructure (E″) of the organosilicon compound.

Although there are no particular restrictions on the reactiontemperature, provided it is a temperature at which the organooxylationreaction proceeds satisfactorily, the temperature is typically within arange from 50 to 80° C., and preferably from 60 to 70° C.

EXAMPLES

A description of specifics of the present invention is provided belowbased on a series of synthesis examples and examples, although thepresent invention is in no way limited by the examples presented below.In the examples, GC is an abbreviation for Gas Chromatography, NMR is anabbreviation for Nuclear Magnetic Resonance spectroscopy, IR is anabbreviation for Infra Red spectroscopy, and bp is an abbreviation forboiling point.

Synthesis Example 1

A 2-liter autoclave fitted with a stirrer, a thermometer and a heaterwas charged with 488.5 g (3.7 mols) of dicyclopentadiene, 1074.7 g (8.9mols) of allyl bromide and 3.1 g of hydroquinone, and the resultingmixture was stirred under heating at 150° C., under sealed conditionsand at normal pressure. After 20 hours, GC was used to confirm that theraw material peaks had disappeared and a new peak attributable to thereaction product had appeared, and the reaction was halted at thispoint. The reaction product was distilled under reduced pressure,yielding a pale yellow transparent liquid (bp: 54 to 56° C., 3 mmHg) ata yield of 70%. GC confirmed that the purity of the reaction product was98%. Furthermore, ¹H NMR and ¹³C NMR confirmed that the reaction productwas 5-bromomethyl-2-norbornene, and was a mixture of the endo and exoisomers.

¹H NMR (300 MHz, CDCl₃, δ (ppm)): main isomer (the endo isomer) 0.56 (m,1H), 1.27 (d, J=8.2 Hz, 1H), 1.45 (m, 1H), 1.91 (m, 1H), 2.48 (m, 1H),2.84 (s, 1H), 2.96 (s, 1H), 3.00 (dd, J=6.9 Hz, 9.6 Hz, 1H), 3.17 (dd,J=6.9 Hz, 9.6 Hz, 1H), 5.96 (m, 1H), 6.17 (m, 1H).

¹³C NMR (75 MHz, CDCl₃, δ (ppm)): main isomer (the endo isomer) 32.6,38.0, 42.0, 43.0, 45.3, 49.5, 131.4, 138.0.

Synthesis Example 2

With the exceptions of using 679.5 g (8.9 mols) of allyl chlorideinstead of the 1074.7 g (8.9 mols) of allyl bromide used in thesynthesis example 1, and altering the quantity of hydroquinone from 3.1g to 2.4 g, reaction and subsequent distillation under reduced pressurewere conducted in the same manner as the synthesis example 1, yielding acolorless transparent liquid (bp: 80 to 82° C., 50 mmHg) at a yield of57%. GC confirmed that the purity of the reaction product was 98%.Furthermore, ¹H NMR and ¹³C NMR confirmed that the reaction product was5-chloromethyl-2-norbornene, and was a mixture of the endo and exoisomers.

¹H NMR (300 MHz, CDCl₃, δ (ppm)): main isomer (the endo isomer) 0.56 (m,1H), 1.27 (d, J=8.2 Hz, 1H), 1.45 (m, 1H), 1.91 (m, 1H), 2.48 (m, 1H),2.84 (s, 1H), 2.96 (s, 1H), 3.00 (dd, J=6.9 Hz, 9.6 Hz, 1H), 3.17 (dd,J=6.9 Hz, 9.6 Hz, 1H), 5.96 (m, 1H), 6.17 (m, 1H).

¹³C NMR (75 MHz, CDCl₃, δ (ppm)): main isomer (the endo isomer) 31.2,41.8, 42.6, 44.5, 48.5, 49.3, 131.6, 137.9.

Example 1

A 1-liter separable flask fitted with a stirrer, a reflux condenser, adropping funnel and a thermometer was charged with 150 g (0.802 mols) of5-bromomethyl-2-norbornene, 45.6 mg of dichloro(1,5-cyclooctadiene)palladium and 89.6 mg of tricyclohexylphosphine, and the mixture washeated to 135° C. Once the internal temperature had stabilized, 130.4 g(0.963 mols) of trichlorosilane was added dropwise over a period of 4hours. Following completion of the dropwise addition, the reactionmixture was stirred at 135° C. After 2 hours, GC was used to confirmthat the raw material peak had disappeared and a new peak attributableto the reaction product had appeared, and the hydrosilylation reactionwas halted at this point. The temperature of the reaction mixture wasthen cooled to 80° C., and 61.6 g (1.92 mols) of methanol was addeddropwise to the mixture. Following completion of the dropwise addition,the reaction mixture was stirred for one hour at 75° C. Subsequently,69.3 g (1.16 mols) of urea was added to the reaction mixture, and afurther 46.2 g (1.44 mols) of methanol was added dropwise. The reactionmixture was stirred for a further 2 hours at 75° C., and the stirringand heating were then halted. Upon standing, the reaction mixtureseparated into a layer containing a methanol solution of ureahydrochloride and a layer containing the reaction product. The layercontaining the reaction product was collected, and then analyzed by GC.This analysis confirmed that the raw material peak had disappeared and anew peak attributable to the reaction product had appeared, and themethoxylation reaction was halted at this point. The reaction productwas distilled under reduced pressure, yielding a colorless transparentliquid (bp: 110 to 116° C., 3 to 5 mmHg) at a yield of 93%. GC confirmedthat the purity of the reaction product was 95%. Furthermore, ¹H NMR,¹³C NMR and ²⁹Si NMR confirmed that the reaction product was5-bromomethyl-norbornyltrimethoxysilane, was a mixture of endo and exoisomers, and was a mixture of an isomer in which the trimethoxysilylgroup was bonded directly to position 2 on the norbornane skeletonstructure and an isomer in which the trimethoxysilyl group was bondeddirectly to position 3 on the norbornane skeleton structure. The NMRspectra of this reaction product are shown in FIG. 1 to FIG. 3.

¹H NMR (300 MHz, CDCl₃, δ (ppm)): isomeric mixture 0.45 to 3.27 (m,12H), 3.35 (s, 6H, Si—OCH₃), 3.37 (s, 3H, Si—OCH₃).

¹³C NMR (75 MHz, CDCl₃, δ (ppm)): isomeric mixture (main product onlylisted) 14.2, 23.4, 24.4, 36.1, 38.2, 39.0, 39.8, 42.2, 50.2 (Si—OCH₃).

²⁹Si NMR (60 MHz, CDCl₃, δ (ppm)): isomeric mixture −45.1, −45.5, −45.8,−46.4.

Example 2

With the exceptions of using 40 mg of a platinum complex composed ofvinyldimethyldisiloxane coordinated to chloroplatinic acid as thehydrosilylation catalyst instead of the 45.6 mg ofdichloro(1,5-cyclooctadiene) palladium used in the example 1, not usingthe tricyclohexylphosphine, and altering the temperature prior to thedropwise addition of the trichlorosilane from 135° C. to 120° C., ahydrosilylation reaction, methoxylation reaction, and distillation underreduced pressure were conducted in the same manner as the example 1,yielding a colorless transparent liquid (bp: 110 to 116° C., 3 to 5mmHg) at a yield of 67%. GC confirmed that the purity of the reactionproduct was 95%. Furthermore, ¹H NMR, ¹³C NMR and ²⁹Si NMR confirmedthat the reaction product was 5-bromomethyl-norbornyltrimethoxysilane,was a mixture of endo and exo isomers, and was a mixture of an isomer inwhich the trimethoxysilyl group was bonded directly to position 2 on thenorbornane skeleton structure and an isomer in which the trimethoxysilylgroup was bonded directly to position 3 on the norbornane skeletonstructure. The NMR spectra of this reaction product were the same asthose shown in FIG. 1 to FIG. 3.

Example 3

A 1-liter separable flask fitted with a stirrer, a reflux condenser, adropping funnel and a thermometer was charged with 290 g (2.03 mols) of5-chloromethyl-2-norbornene, 0.32 g of dichloro(1,5-cyclooctadiene)palladium and 0.62 g of tricyclohexylphosphine, and the mixture washeated to 135° C. Once the internal temperature had stabilized, 302 g(2.23 mols) of trichlorosilane was added dropwise over a period of 4hours. Following completion of the dropwise addition, the reactionmixture was stirred at 135° C. After 2 hours, GC was used to confirmthat the raw material peak had disappeared and a new peak attributableto the reaction product had appeared, and the hydrosilylation reactionwas halted at this point. The temperature of the reaction mixture wasthen cooled to 80° C., and 142.7 g (4.46 mols) of methanol was addeddropwise to the mixture. Following completion of the dropwise addition,the reaction mixture was stirred for one hour at 75° C. Subsequently,160.6 g (2.67 mols) of urea was added to the reaction mixture, and afurther 107.0 g (3.35 mols) of methanol was added dropwise. The reactionmixture was stirred for a further 2 hours at 75° C., and the stirringand heating were then halted. Upon standing, the reaction mixtureseparated into a layer containing a methanol solution of ureahydrochloride and a layer containing the reaction product. The layercontaining the reaction product was collected, and then analyzed by GC.This analysis confirmed that the raw material peak had disappeared and anew peak attributable to the reaction product had appeared, and themethoxylation reaction was halted at this point. The reaction productwas distilled under reduced pressure, yielding a colorless transparentliquid (bp: 106 to 108° C., 3 to 5 mmHg) at a yield of 92%. GC confirmedthat the purity of the reaction product was 95%. Furthermore, ¹H NMR,¹³C NMR and ²⁹Si NMR confirmed that the reaction product was5-chloromethyl-norbornyltrimethoxysilane, was a mixture of endo and exoisomers, and was a mixture of an isomer in which the trimethoxysilylgroup was bonded directly to position 2 on the norbornane skeletonstructure and an isomer in which the trimethoxysilyl group was bondeddirectly to position 3 on the norbornane skeleton structure. The NMRspectra of this reaction product are shown in FIG. 4 to FIG. 6.

¹H NMR (300 MHz, CDCl₃, δ (ppm)): isomeric mixture 0.45 to 3.26 (m,12H), 3.38 (s, 6H, Si—OCH₃), 3.39 (s, 3H, Si—OCH₃).

¹³C NMR (75 MHz, CDCl₃, δ (ppm)): isomeric mixture (main product onlylisted) 14.4, 23.7, 24.5, 37.0, 37.9, 38.9, 42.2, 46.9, 50.3 (Si—OCH₃).

²⁹Si NMR (60 MHz, CDCl₃, δ (ppm)): isomeric mixture −45.1, −45.6, −45.9,−46.5.

Example 4

With the exceptions of using 40 mg of a platinum complex composed ofvinyldimethyldisiloxane coordinated to chloroplatinic acid as thehydrosilylation catalyst instead of the 0.32 g ofdichloro(1,5-cyclooctadiene) palladium used in the example 3, not usingthe tricyclohexylphosphine, and altering the temperature prior to thedropwise addition of the trichlorosilane from 135° C. to 120° C., ahydrosilylation reaction, methoxylation reaction, and distillation underreduced pressure were conducted in the same manner as the example 3,yielding a colorless transparent liquid (bp: 106 to 108° C., 3 to 5mmHg) at a yield of 66%. GC confirmed that the purity of the reactionproduct was 95%. Furthermore, ¹H NMR, ¹³C NMR and ²⁹Si NMR confirmedthat the reaction product was 5-chloromethyl-norbornyltrimethoxysilane,was a mixture of endo and exo isomers, and was a mixture of an isomer inwhich the trimethoxysilyl group was bonded directly to position 2 on thenorbornane skeleton structure and an isomer in which the trimethoxysilylgroup was bonded directly to position 3 on the norbornane skeletonstructure. The NMR spectra of this reaction product were the same asthose shown in FIG. 4 to FIG. 6.

Example 5

A 1-liter separable glass flask fitted with a thermometer, awater-cooled condenser and a dropping funnel was charged with 110 g (1.0mols) of potassium acrylate, 200 g of dimethylformamide, 200 g oftoluene and 2.7 g of bis-t-butylhydroxytoluene, the resulting mixturewas heated to 140° C., and the water contained within the toluene andpotassium acrylate was distilled and removed from the reaction system.Subsequently, the temperature was lowered to 110° C., and 309 g (1.0mols) of 5-bromomethyl-norbornyltrimethoxysilane was added dropwise tothe reaction system. The reaction mixture was then refluxed at 110° C.under constant stirring, while the progress of the reaction was trackedusing GC. After 5 hours, GC confirmed that the peak attributable to theraw material methoxysilane had disappeared completely, and a new peakattributable to the reaction product had appeared, and the reaction washalted at this point. Subsequently, the generated potassium bromide wasremoved by filtration, the reaction solvent was then removed byevaporation under reduced pressure, and the product was then purified bydistillation under reduced pressure, yielding a colorless transparentliquid (purified yield: 43%). GC confirmed that the purity of thereaction product was at least 94%. Furthermore, the ¹H NMR, ¹³C NMR,²⁹Si NMR and IR spectra confirmed that the reaction product was5-acryloyloxymethyl-norbornyltrimethoxysilane, was a mixture of endo andexo isomers, and was a mixture of an isomer in which the trimethoxysilylgroup was bonded directly to position 2 on the norbornane skeletonstructure and an isomer in which the trimethoxysilyl group was bondeddirectly to position 3 on the norbornane skeleton structure. The NMRspectra of this reaction product are shown in FIG. 7 to FIG. 9, and theIR spectrum is shown in FIG. 10.

¹H NMR (300 MHz, CDCl₃, δ (ppm)): isomeric mixture 0.43 to 3.22 (m,12H), 3.32 (s, 9H, Si—OCH₃), 5.57 to 6.15 (m, 3H, acrylic group)

¹³C NMR (75 MHz, CDCl₃, δ (ppm)): isomeric mixture (main product onlylisted) 14.6, 24.0, 24.2, 36.7, 37.4, 38.8, 40.6, 50.1 (Si—OCH₃), 67.2,128.2, 129.7, 165.4.

²⁹Si NMR (60 MHz, CDCl₃, δ (ppm)): isomeric mixture −44.9, −45.6, −45.9,−46.3.

Example 6

With the exception of using 124 g (1.0 mols) of potassium methacrylateinstead of the 110 g (1.0 mols) of potassium acrylate used in theexample 5, a colorless transparent liquid (purified yield: 35%) wasproduced in the same manner as the example 5. GC confirmed that thepurity of the reaction product was at least 93%. Furthermore, the ¹HNMR, ¹³C NMR, ²⁹Si NMR and IR spectra confirmed that the reactionproduct was 5-methacryloyloxymethyl-norbornyltrimethoxysilane, was amixture of endo and exo isomers, and was a mixture of an isomer in whichthe trimethoxysilyl group was bonded directly to position 2 on thenorbornane skeleton structure and an isomer in which the trimethoxysilylgroup was bonded directly to position 3 on the norbornane skeletonstructure.

¹H NMR (300 MHz, CDCl₃, δ (ppm)): isomeric mixture 0.41 to 3.25 (m,12H), 1.96 (s, 3H), 3.30 (s, 9H, Si—OCH₃), 5.55 to 6.10 (m, 2H,methacrylic group)

¹³C NMR (75 MHz, CDCl₃, δ (ppm)): isomeric mixture (main product onlylisted) 14.3, 18.1, 23.8, 24.7, 36.3, 37.4, 38.2, 40.8, 50.9 (Si—OCH₃),66.2, 125.2, 136.7, 167.4.

²⁹Si NMR (60 MHz, CDCl₃, δ (ppm)): isomeric mixture −44.8, −45.1, −45.7,−46.8.

1. A method of producing a radiation-polymerizable functionalgroup-containing organosilicon compound comprising (A) a norbornaneskeleton structure, (B) a hydrolyzable silyl group bonded directly tothe norbornane skeleton structure, and (C) a radiation-polymerizablefunctional group bonded to the norbornane skeleton structure, eitherdirectly or via a carbon atom, a hetero atom, or a combination thereof,the method comprising: reacting a haloalkyl group-containingorganosilicon compound, comprising (D) a norbornane skeleton structure,(E) a hydrolyzable silyl group bonded directly to the norbornaneskeleton structure, and (F) a haloalkyl group, which is bonded directlyto the norbornane skeleton structure, and either contains or does notcontain a hetero atom, with at least one salt having aradiation-polymerizable functional group, selected from the groupconsisting of alkali metal salts of organic acids having aradiation-polymerizable functional group and alkaline earth metal saltsof organic acids having a radiation-polymerizable functional group, at atemperature within a range from 50 to 150° C.
 2. The method according toclaim 1, wherein the haloalkyl group-containing organosilicon compoundis represented by a general formula (4) shown below:

wherein, each X represents, independently, a halogen atom, an alkoxygroup of 1 to 10 carbon atoms, a phenyloxy group, or an acetoxy group,R¹ represents an alkyl group of 1 to 10 carbon atoms, R² represents analkylene group of 1 to 10 carbon atoms that either contains, or does notcontain, an oxygen atom, a sulfur atom, a nitrogen atom, or acombination thereof, m represents an integer from 0 to 2, and Zrepresents a halogen atom, the salt having a radiation-polymerizablefunctional group is represented by a general formula (10) shown below:Y-M  (10) wherein, Y represents an acryloyloxy group or amethacryloyloxy group, and M represents an alkali metal atom or analkaline earth metal atom, and the radiation-polymerizable functionalgroup-containing organosilicon compound is represented by a generalformula (1) shown below:

wherein, X, Y, R¹, R² and m are as defined above.
 3. The methodaccording to claim 2, wherein the haloalkyl group-containingorganosilicon compound represented by the general formula (4) isrepresented by a general formula (5) shown below:

wherein, X, Z, R¹ and m are as defined above, and n represents aninteger from 1 to 10, and the radiation-polymerizable functionalgroup-containing organosilicon compound represented by the generalformula (1) is represented by a general formula (2) shown below:

wherein, X, Y, R¹, m and n are as defined above.
 4. The method accordingto claim 3, wherein the haloalkyl group-containing organosiliconcompound represented by the general formula (5) is represented by ageneral formula (6) shown below:

wherein, X, R¹ and m are as defined above, and Z′ represents a bromineatom or a chlorine atom, and the radiation-polymerizable functionalgroup-containing organosilicon compound represented by the generalformula (2) is represented by a general formula (3) shown below:

wherein, X, Y, R¹ and m are as defined above.